US8044244B2 - Process for preparing aromatic amines in a fluidized-bed reactor - Google Patents

Process for preparing aromatic amines in a fluidized-bed reactor Download PDF

Info

Publication number
US8044244B2
US8044244B2 US12/441,907 US44190707A US8044244B2 US 8044244 B2 US8044244 B2 US 8044244B2 US 44190707 A US44190707 A US 44190707A US 8044244 B2 US8044244 B2 US 8044244B2
Authority
US
United States
Prior art keywords
fluidized
cells
process according
internals
bed reactor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related, expires
Application number
US12/441,907
Other languages
English (en)
Other versions
US20100048955A1 (en
Inventor
Lothar Seidemann
Lucia KOENIGSMANN
Christian Schneider
Ekkehard Schwab
Dieter Stuetzer
Celine Liekens
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Assigned to BASF SE reassignment BASF SE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: STUETZER, DIETER, SCHNEIDER, CHRISTIAN, SCHWAB, EKKEHARD, KOENIGSMANN, LUCIA, LIEKENS, CELINE, SEIDEMANN, LOTHAR
Publication of US20100048955A1 publication Critical patent/US20100048955A1/en
Application granted granted Critical
Publication of US8044244B2 publication Critical patent/US8044244B2/en
Expired - Fee Related legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/32—Packing elements in the form of grids or built-up elements for forming a unit or module inside the apparatus for mass or heat transfer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/005—Separating solid material from the gas/liquid stream
    • B01J8/006—Separating solid material from the gas/liquid stream by filtration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1836—Heating and cooling the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1845—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with particles moving upwards while fluidised
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1872—Details of the fluidised bed reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/34—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with stationary packing material in the fluidised bed, e.g. bricks, wire rings, baffles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/45—Monoamines
    • C07C211/46—Aniline
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/14—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles
    • C10G45/20—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles according to the "fluidised-bed" technique
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
    • B01J2208/00132—Tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
    • B01J2219/322—Basic shape of the elements
    • B01J2219/32203—Sheets
    • B01J2219/3221—Corrugated sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
    • B01J2219/322—Basic shape of the elements
    • B01J2219/32203—Sheets
    • B01J2219/32213—Plurality of essentially parallel sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
    • B01J2219/322—Basic shape of the elements
    • B01J2219/32203—Sheets
    • B01J2219/32213—Plurality of essentially parallel sheets
    • B01J2219/3222—Plurality of essentially parallel sheets with sheets having corrugations which intersect at an angle different from 90 degrees
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
    • B01J2219/322—Basic shape of the elements
    • B01J2219/32203—Sheets
    • B01J2219/32224—Sheets characterised by the orientation of the sheet
    • B01J2219/32227—Vertical orientation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
    • B01J2219/324—Composition or microstructure of the elements
    • B01J2219/32408—Metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
    • B01J2219/324—Composition or microstructure of the elements
    • B01J2219/32408—Metal
    • B01J2219/32416—Metal fibrous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
    • B01J2219/324—Composition or microstructure of the elements
    • B01J2219/32466—Composition or microstructure of the elements comprising catalytically active material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
    • B01J2219/324—Composition or microstructure of the elements
    • B01J2219/32466—Composition or microstructure of the elements comprising catalytically active material
    • B01J2219/32475—Composition or microstructure of the elements comprising catalytically active material involving heat exchange

Definitions

  • the invention relates to a process for preparing aromatic amines by catalytic hydrogenation of the corresponding nitro compounds in a fluidized-bed reactor, in particular for preparing aniline by catalytic hydrogenation of nitrobenzene.
  • DE-A 2 849 002 discloses a process for the catalytic gas-phase hydrogenation of aromatic amines over palladium-comprising supported catalysts which is preferably carried out in tube reactors, in which the heat of reaction is removed by means of a suitable heat transfer fluid whose temperature is kept in a range from about 150 to 350° C.
  • a disadvantage is the limited heat removal which is possible: the possible heat fluxes for the removal of heat of reaction by means of a heat transfer medium are in the range from 0.5 to 5 kW per square meter for fixed-bed supported catalysts, so that in the case of strong exothermic reactions, especially the hydrogenation of nitrobenzene to aniline, the removal of the heat of reaction comes up against difficulties when using a tube reactor.
  • hydrogenation catalysts are the heavy metals of groups 1 and 5 to 7 of the Periodic Table and also the iron and platinum group, for example copper, molybdenum, tungsten, nickel, cobalt or mixtures thereof, and their oxides, sulfides or halides, if appropriate together with boron or boron compounds.
  • the catalysts can be applied to various supports.
  • the catalysts have a small particle size, for example 0.3 mm, and are kept in swirling motion by the starting mixture to be hydrogenated and the hydrogen necessary for the hydrogenation, if appropriate, in admixture with an inert gas.
  • the process of the main patent DE-A 114 820 is carried out under atmospheric pressure, unlike the process of the supplementary patent DE-A 1 133 194 which is carried out at an elevated pressure of at least 3 atmospheres gauge pressure, with a longer life of the catalyst being said to be achieved.
  • the fluidized-bed reactor Owing to the very good heat removal properties of a fluidized bed, where heat fluxes in the range from 10 to 100 W per square meter can be achieved for the removal of heat of reaction, the fluidized-bed reactor can be designed considerably more easily for the favored isothermal reaction mode compared to tube reactors which have to be cooled in a complicated fashion.
  • a fluidized bed has disadvantages in terms of mass transfer, since the contact between catalyst and reactants is limited in a known way by the formation of gas bubbles comprising little solid. As a result, part of the aromatic nitro compounds does not come into contact with the swirling supported catalyst and it leaves the reaction zone unreacted. This not only reduces the conversion but also results in further disadvantages: for example, unreacted nitrobenzene in the aniline interferes in the preparation of diphenylmethanediisocyanate (MDI), which is an important intermediate in the polyurethane value-added chain.
  • MDI diphenylmethanediisocyanate
  • the object is achieved by a process for preparing aromatic amines by catalytic hydrogenation of the corresponding nitro compound in a fluidized-bed reactor, in which a gaseous reaction mixture comprising the nitro compound and hydrogen flows from the bottom upward through a heterogeneous particulate catalyst forming a fluidized bed, wherein the fluidized bed is provided with internals which divide the fluidized bed into a plurality of cells arranged horizontally in the fluidized-bed reactor and a plurality of cells arranged vertically in the fluidized-bed reactor, with the cells having cell walls which are permeable to gas and have openings which ensure an exchange number of the heterogeneous, particulate catalyst in the vertical direction in the range from 1 to 100 liters/hour per liter of reactor volume.
  • the fluidized bed into cells, i.e. hollow spaces enclosed by cell walls, by means of internals both in the horizontal direction and in the vertical direction, with the cell walls being permeable to gas and having openings which allow solids exchange in the vertical direction in the fluidized-bed reactor. Furthermore, the cell walls can be provided with openings which allow solids exchange in the horizontal direction.
  • the heterogeneous particulate catalyst can thus move in the vertical direction and possibly also in the horizontal direction through the fluidized-bed reactor, but is held back in the individual cells compared to a fluidized bed without these, with the above-defined exchange numbers being ensured.
  • the exchange number is determined by the use of radioactively labeled solid tracer particles which are introduced into the fluidized reaction system, as described, for example, in: G. Reed “Radioisotope techniques for problem-solving in industrial process plants”, Chapter 9 (“Measurement of residence times and residence-time distribution”), p. 112-137, (J. S. Charlton, ed.), Leonard Hill, Glasgow and London 1986, (ISBN 0-249-44171-3). Recording of the time and location of these radioactively labeled particles enables the solids motion to be determined locally and the exchange number to be derived (G. Reed in: “Radioisotope techniques for problem-solving in industrial process plants”, Chapter 11 (“Miscellaneous radiotracer applications”, 11.1. “Mixing and blending studies”), p. 167-176, (J. S. Chariton, ed.), Leonard Hill, Glasgow and London 1986, (ISBN 0-249-44171-3).
  • Targeted selection of the geometry of the cells enables the residence time of the heterogeneous particulate catalyst in these to be matched to the characteristics of the reaction to be carried out in the particular case.
  • the series arrangement of a plurality of cells i.e., in particular from 0 to 100 cells or else from 10 to 50 cells, per meter of bed height, i.e. in the vertical direction in the direction of gas flow from the bottom upward through the reactor, limits backmixing and thus improves the selectivity and the conversion.
  • the additional arrangement of a plurality of cells i.e. from 10 to 100 cells or else from 10 to 50 cells, per meter in the horizontal direction in the fluidized-bed reactor, i.e. cells through which the reaction mixture flows in parallel or in series, allows the capacity of the reactor to be matched to requirements.
  • the capacity of the reactor of the invention is thus not limited and can be matched to specific requirements, for example for reactions on an industrial scale.
  • the cell material itself takes up only a limited part of the cross section of the fluidized-bed reactor, in particular only from about 1 to 10% of the cross-sectional area of the fluidized-bed reactor, and therefore does not lead to the disadvantages associated with increased occupation of the cross section which are known in the case of the internals from the prior art.
  • the fluidized-bed reactor used in the process of the invention is, as is customary, supplied with the gaseous starting materials from the bottom via a gas distributor.
  • the gaseous starting materials are partially reacted over the heterogeneous particulate catalyst which is fluidized by the gas flow.
  • the partially reacted starting materials flow into the next cell where they undergo a further partial reaction.
  • the reaction zone there is a solids separation device which separates the entrained catalyst from the gas phase.
  • the reacted product leaves the fluidized-bed reactor according to the invention at its upper end in solids-free form.
  • the fluidized-bed reactor used according to the invention can be additionally supplied with liquid starting materials either from the bottom or from the side. However, these have to be able to vaporize immediately at the point where they are introduced in order to ensure the fluidizability of the catalyst.
  • the aromatic amine prepared by the process of the invention is preferably aniline and the corresponding nitro compound is therefore preferably nitrobenzene.
  • catalysts it is possible to use the known, particulate, supported or unsupported catalysts for the hydrogenation of aromatic amines, in particular catalysts comprising heavy metals of the first and/or fifth to eighth group of the Periodic Table, preferably one or more of the elements copper, palladium, molybdenum, tungsten, nickel and cobalt.
  • the geometry of the cells is not restricted; the cells can be, for example, cells having round walls, in particular hollow spheres, or cells having angular walls. If the walls are angular, the cells preferably have no more than 50 corners, preferably no more than 30 corners and in particular no more than 10 corners.
  • the cell walls in the cells of the internals are permeable to gas so as to ensure fluidization of the heterogeneous particulate catalyst as a result of flow of the gas phase through the cells.
  • the cell walls can be made of a woven mesh or else of sheet-like materials which have, for example, round holes or holes of another shape.
  • the mean mesh opening of the woven meshes used or the preferred width of the holes in the cell walls is, in particular, from 50 to 1 mm, more preferably from 10 to 1 mm and particularly preferably from 5 to 1 mm.
  • cross-channel packings i.e. packings having creased gas-permeable metal sheets, expanded metal sheets or woven meshes which are arranged in parallel to one another in the vertical direction in the fluidized-bed reactor and have creases which form flat areas between the creases having an angle of inclination to the vertical which is different from zero, with the flat areas between the creases of successive metal sheets, expanded metal sheets or woven meshes having the same angle of inclination but with the opposite sign so as to form cells which are delimited in the vertical direction by constrictions between the creases.
  • cross-channel packings i.e. packings having creased gas-permeable metal sheets, expanded metal sheets or woven meshes which are arranged in parallel to one another in the vertical direction in the fluidized-bed reactor and have creases which form flat areas between the creases having an angle of inclination to the vertical which is different from zero, with the flat areas between the creases of successive metal sheets, expanded metal sheets or woven meshes having the same angle
  • cross-channel packings are the packings of the types Mellpack®, CY or BX from Sulzer AG, CH-8404 Winterthur, or the types A3, BSH, B1 or M from Monz GmbH, D-40723 Hilden.
  • the mean hydraulic diameter of the cells is preferably in the range from 500 to 1 mm, more preferably from 100 to 5 mm and particularly preferably from 50 to 5 mm.
  • the hydraulic diameter is defined in a known manner as four times the horizontal cross-sectional area of the cell divided by the circumference of the cell viewed from above.
  • the mean height of the cells is preferably from 100 to 1 mm, more preferably from 100 to 3 mm and particularly preferably from 40 to 5 mm.
  • cross-channel packings occupy only a small part of the cross-sectional area of the fluidized-bed reactor, in particular a proportion of from about 1 to 10% of this.
  • angles of inclination to the vertical of the flat areas between the creases are preferably in the range from 10 to 80°, in particular from 20 to 70°, particularly preferably from 30 to 60°.
  • the flat areas between the creases in the metal sheets, expanded metal sheets or woven meshes preferably have a crease height in the range from 100 to 3 mm, particularly preferably from 40 to 5 mm, and a spacing of the constrictions between the creases in the range from 50 to 2 mm, particularly preferably from 20 to 3 mm.
  • heat exchangers can be installed in the internals forming the cells for the purpose of introducing heat in the case of endothermic reactions or removing heat in the case of exothermic reactions.
  • the heat exchangers can, for example, be configured in the form of plates or tubes and be arranged vertically, horizontally or in an inclined fashion in the fluidized-bed reactor.
  • the heat transfer areas can be matched to the specific reaction; in this way, any reaction can be implemented in heat engineering terms by means of the reactor concept according to the invention.
  • the internals forming the cells are preferably made of materials having a very good thermal conductivity so that heat transport via the cell walls is not hindered.
  • the heat transfer properties of the reactor according to the invention must correspond to those of a conventional fluidized-bed reactor.
  • the materials for the internals forming the cells should also have a sufficient stability under reaction conditions; in particular, not only the resistance to chemical and thermal stresses but also the resistance of the material to mechanical attack by the fluidized catalyst have to be taken into account.
  • metal, ceramic, polymers or glass materials are particularly useful.
  • the internals are preferably configured so that they divide from 10 to 90% by volume of the fluidized bed into cells.
  • the lower region of the fluidized bed in the flow direction of the gaseous reaction mixture is preferably free of internals.
  • the internals which divide the fluidized bed into cells are particularly preferably located above the heat exchanger. This enables, in particular, the residue conversion to be increased.
  • the reactor according to the invention does not have any disadvantages in respect of demixing and discharge tendency of the fluidized particulate catalyst.
  • FIG. 1 schematically shows a preferred embodiment of a fluidized-bed reactor used according to the invention
  • FIG. 2 schematically shows a preferred embodiment of internals used according to the invention.
  • the fluidized-bed reactor 1 shown in FIG. 1 comprises a solids-free gas distributor zone 2 , internals 3 which form cells 4 and a heat exchanger 5 in the region of the internals 3 .
  • the reactor widens and has at least one solids separator 6 .
  • the arrow 7 indicates the introduction of the gaseous starting materials and the arrow 8 indicates the discharge of the gaseous product stream. Additional liquid-phase starting materials can be introduced at the side, via the broken-line arrows 9 .
  • FIG. 2 shows a preferred embodiment of internals 3 according to the invention in the form of a cross-channel packing having creased metal sheets 10 which are arranged parallel to one another in the longitudinal direction and have creases 11 which divide the metal sheet 10 into flat areas 12 between the creases, with two successive metal sheets being arranged so that they have the same angle of inclination but with the opposite sign and thus form cells 4 which are delimited in the vertical direction by constrictions 13 .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US12/441,907 2006-09-19 2007-09-14 Process for preparing aromatic amines in a fluidized-bed reactor Expired - Fee Related US8044244B2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP06120885 2006-09-19
EP06120885.6 2006-09-19
EP06120885 2006-09-19
PCT/EP2007/059703 WO2008034770A1 (de) 2006-09-19 2007-09-14 Verfahren zur herstellung von aromatischen aminen in einem wirbelschichtreaktor

Publications (2)

Publication Number Publication Date
US20100048955A1 US20100048955A1 (en) 2010-02-25
US8044244B2 true US8044244B2 (en) 2011-10-25

Family

ID=39017072

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/441,907 Expired - Fee Related US8044244B2 (en) 2006-09-19 2007-09-14 Process for preparing aromatic amines in a fluidized-bed reactor

Country Status (10)

Country Link
US (1) US8044244B2 (de)
EP (1) EP2069283B1 (de)
JP (1) JP5389655B2 (de)
KR (1) KR20090061050A (de)
CN (1) CN101528663B (de)
AT (1) ATE472522T1 (de)
DE (1) DE502007004280D1 (de)
ES (1) ES2347606T3 (de)
PT (1) PT2069283E (de)
WO (1) WO2008034770A1 (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9290438B2 (en) 2012-04-16 2016-03-22 Bayer Materialscience Ag Method for starting a reaction during the production of aromatic amines from nitroaromatics
US9469594B2 (en) 2012-04-16 2016-10-18 Covestro Deutschland Ag Method for stopping a reaction during the production of aromatic amines from nitroaromatics
US10513487B2 (en) 2014-06-24 2019-12-24 Covestro Deutschland Ag Methods for producing chemical products with operation interruptions
US10618871B2 (en) 2016-08-17 2020-04-14 Covestro Deutschland Ag Process for producing isocyanate and at least one further chemical product in an integrated production

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009019436A1 (de) 2009-04-29 2010-11-04 Bayer Materialscience Ag Verfahren zur Herstellung von aromatischen Aminen
CN102421744B (zh) 2009-05-14 2015-04-08 巴斯夫欧洲公司 制备芳族胺的方法
US8703997B2 (en) 2009-10-20 2014-04-22 Basf Se Process for preparation and preferably distillative workup of diphenylmethane diisocyanate (MDI)
EP2641892A1 (de) 2012-03-23 2013-09-25 Bayer MaterialScience AG Verfahren zur Reinigung von Anilin aus Gasphasenhydrierungen
WO2015132200A1 (de) * 2014-03-05 2015-09-11 Basf Se Verfahren zur kombinierten herstellung von aromatischen kohlenwasserstoffen und aromatischen aminokohlenwasserstoffen
CN111054271B (zh) * 2018-10-17 2021-03-26 中国石油化工股份有限公司 低剂耗的硝基苯加氢制苯胺反应装置及反应方法
WO2020207874A1 (de) 2019-04-12 2020-10-15 Basf Se Katalysatorsystem für die herstellung von aromatischen aminen

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1114820B (de) 1960-01-15 1961-10-12 Basf Ag Verfahren zur Herstellung von Anilin
DE1133394B (de) 1961-01-18 1962-07-19 Basf Ag Verfahren zur Herstellung von Anilin durch katalytische Hydrierung von Nitrobenzol
US3136818A (en) 1960-01-15 1964-06-09 Basf Ag Production of aniline
US3429654A (en) * 1964-11-05 1969-02-25 Basf Ag Reacting gases or vapors in a fluidized bed
US3482946A (en) 1966-06-27 1969-12-09 Air Prod & Chem Reactor for contacting vaporous reactants with fluidized solids
DE2849002A1 (de) 1978-11-11 1980-05-22 Bayer Ag Verfahren zur katalytischen hydrierung von nitrobenzol
US4430302A (en) * 1982-04-12 1984-02-07 Uop Inc. Fluidized catalyst regeneration apparatus
EP0331465A1 (de) 1988-03-01 1989-09-06 MITSUI TOATSU CHEMICALS, Inc. Chlorerzeugungsverfahren
EP0428265A1 (de) 1989-11-13 1991-05-22 Koch Engineering Company Inc Verfahren und Einbauten zur Durchführung katalytischer Reaktionen in Destillationskolonneneinbauten
US20030106837A1 (en) * 2001-12-06 2003-06-12 Gerd Kaibel Heterogeneously catalyzed reactions and apparatus therefor
DE10226120A1 (de) 2002-06-12 2003-12-24 Basf Ag Geträgerte Metalloxide als Katalysatoren für Aldolkondensationen
EP1477224A1 (de) 2003-05-16 2004-11-17 Sulzer Chemtech AG Verwendung einer Kreuzkanalpackung aus Metallgewebe
WO2005077520A1 (de) 2004-02-11 2005-08-25 Basf Aktiengesellschaft Reaktor und verfahren zur herstellung von chlor aus hcl
DE102004014677A1 (de) 2004-03-25 2005-10-13 Basf Ag Wirbelschichtverfahren und Reaktor zur Durchführung exothermer chemischer Gleichgewichtsreaktionen
US7098366B2 (en) 2001-12-06 2006-08-29 Basf Aktiengesellschaft Supported metal oxides as catalysts for aldol condensations
US7476297B2 (en) 2001-12-06 2009-01-13 Basf Se Device and method for carrying out heterogeneously-catalysed reactive distillations in particular for the production of pseudoionone

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52129682A (en) * 1976-04-26 1977-10-31 Hitachi Ltd Splitting bubble in fluidized bed
JPS57140312A (en) * 1981-02-19 1982-08-30 Osaka Titanium Seizo Kk Manufacture of trichlorosilane
EP0333767A1 (de) * 1986-12-10 1989-09-27 Lummus Crest, Inc. Wirbelbett
FR2728805B1 (fr) * 1994-12-29 1997-03-28 Total Raffinage Distribution Procede et dispositif pour le strippage de solides fluidises et utilisation dans un procede de craquage a l'etat fluide
KR20090080043A (ko) * 2006-09-19 2009-07-23 바스프 에스이 기상 반응을 수행하기 위한 유동층 반응기

Patent Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1114820B (de) 1960-01-15 1961-10-12 Basf Ag Verfahren zur Herstellung von Anilin
US3136818A (en) 1960-01-15 1964-06-09 Basf Ag Production of aniline
DE1133394B (de) 1961-01-18 1962-07-19 Basf Ag Verfahren zur Herstellung von Anilin durch katalytische Hydrierung von Nitrobenzol
US3429654A (en) * 1964-11-05 1969-02-25 Basf Ag Reacting gases or vapors in a fluidized bed
US3482946A (en) 1966-06-27 1969-12-09 Air Prod & Chem Reactor for contacting vaporous reactants with fluidized solids
DE2849002A1 (de) 1978-11-11 1980-05-22 Bayer Ag Verfahren zur katalytischen hydrierung von nitrobenzol
US4265834A (en) 1978-11-11 1981-05-05 Bayer Aktiengesellschaft Process for the catalytic hydrogenation of nitrobenzene
US4430302A (en) * 1982-04-12 1984-02-07 Uop Inc. Fluidized catalyst regeneration apparatus
EP0331465A1 (de) 1988-03-01 1989-09-06 MITSUI TOATSU CHEMICALS, Inc. Chlorerzeugungsverfahren
US5112593A (en) 1988-03-01 1992-05-12 Mitsui Toatsu Chemicals, Incorporated Production process of chlorine
US5073236A (en) 1989-11-13 1991-12-17 Gelbein Abraham P Process and structure for effecting catalytic reactions in distillation structure
EP0428265A1 (de) 1989-11-13 1991-05-22 Koch Engineering Company Inc Verfahren und Einbauten zur Durchführung katalytischer Reaktionen in Destillationskolonneneinbauten
US20030106837A1 (en) * 2001-12-06 2003-06-12 Gerd Kaibel Heterogeneously catalyzed reactions and apparatus therefor
US7098366B2 (en) 2001-12-06 2006-08-29 Basf Aktiengesellschaft Supported metal oxides as catalysts for aldol condensations
US7476297B2 (en) 2001-12-06 2009-01-13 Basf Se Device and method for carrying out heterogeneously-catalysed reactive distillations in particular for the production of pseudoionone
DE10226120A1 (de) 2002-06-12 2003-12-24 Basf Ag Geträgerte Metalloxide als Katalysatoren für Aldolkondensationen
EP1477224A1 (de) 2003-05-16 2004-11-17 Sulzer Chemtech AG Verwendung einer Kreuzkanalpackung aus Metallgewebe
US20050249648A1 (en) 2003-05-16 2005-11-10 Florian Kehrer Mass transfer method using static packings
US7434794B2 (en) * 2003-05-16 2008-10-14 Florian Kehrer Mass transfer method using static packings
WO2005077520A1 (de) 2004-02-11 2005-08-25 Basf Aktiengesellschaft Reaktor und verfahren zur herstellung von chlor aus hcl
US20070183963A1 (en) 2004-02-11 2007-08-09 Basf Aktiengesellschaft Reactor and method for producing chlorine from hcl
DE102004014677A1 (de) 2004-03-25 2005-10-13 Basf Ag Wirbelschichtverfahren und Reaktor zur Durchführung exothermer chemischer Gleichgewichtsreaktionen
US20070202035A1 (en) 2004-03-25 2007-08-30 Christian Walsdorff Fluidized Bed Method And Reactor For Carrying Out Exotermic Chemical Equilibruim Reaction

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Diao, Shigang et al., "Gaseous catalytic hydrogenation of nitrobenzene to aniline in a two-stage fluidized bed reactor", Applied Catalysis A: General, Elsevier, vol. 286, pp. 30-35, (2005).

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9290438B2 (en) 2012-04-16 2016-03-22 Bayer Materialscience Ag Method for starting a reaction during the production of aromatic amines from nitroaromatics
US9469594B2 (en) 2012-04-16 2016-10-18 Covestro Deutschland Ag Method for stopping a reaction during the production of aromatic amines from nitroaromatics
US10513487B2 (en) 2014-06-24 2019-12-24 Covestro Deutschland Ag Methods for producing chemical products with operation interruptions
US10618871B2 (en) 2016-08-17 2020-04-14 Covestro Deutschland Ag Process for producing isocyanate and at least one further chemical product in an integrated production

Also Published As

Publication number Publication date
US20100048955A1 (en) 2010-02-25
EP2069283B1 (de) 2010-06-30
KR20090061050A (ko) 2009-06-15
DE502007004280D1 (de) 2010-08-12
JP2010503716A (ja) 2010-02-04
PT2069283E (pt) 2010-08-03
ES2347606T3 (es) 2010-11-02
EP2069283A1 (de) 2009-06-17
CN101528663B (zh) 2012-07-25
JP5389655B2 (ja) 2014-01-15
CN101528663A (zh) 2009-09-09
ATE472522T1 (de) 2010-07-15
WO2008034770A1 (de) 2008-03-27

Similar Documents

Publication Publication Date Title
US8044244B2 (en) Process for preparing aromatic amines in a fluidized-bed reactor
US8038950B2 (en) Fluidized-bed reactor for carrying out a gas-phase reaction
EP2429692A1 (de) Rekator für exotherme und endotherme katalytische reaktionen
EA027094B1 (ru) Способ гидрогалогенирования ненасыщенного углеводорода
US8092747B2 (en) Modular reactor for exothermic/endothermic chemical reactions
US3837822A (en) Two-stage countercurrent fluid-solid contacting process
US8202917B2 (en) Pillow panel reactor and process
US20090269270A1 (en) Process for preparing chlorine in a fluidized-bed reactor
PT2125462E (pt) Método para a produção de aminas aromáticas num reactor de leito fluidizado
CN219580511U (zh) 一种管式固定床反应器
US4734264A (en) Catalytic reactor for the production of methanol, ammonia, synthesis gas and higher alcohols
USRE28648E (en) Process for carrying out chemical reactions in a fluidized bed
WO2008034837A1 (de) Verfahren zur herstellung von 1,2-dichlorethan durch katalytische oxichlorierung von ethen in einem wirbelschichtreaktor

Legal Events

Date Code Title Description
AS Assignment

Owner name: BASF SE,GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SEIDEMANN, LOTHAR;KOENIGSMANN, LUCIA;SCHNEIDER, CHRISTIAN;AND OTHERS;SIGNING DATES FROM 20090529 TO 20090802;REEL/FRAME:023059/0638

Owner name: BASF SE, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SEIDEMANN, LOTHAR;KOENIGSMANN, LUCIA;SCHNEIDER, CHRISTIAN;AND OTHERS;SIGNING DATES FROM 20090529 TO 20090802;REEL/FRAME:023059/0638

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20151025